VIET NAM NATIONAL UNIVERSITY- HCMC
UNIVERSITY OF SCIENCE
ANALYTICAL CHEMISTRY DEPARTMENT
Gas chromatography
MSc. Tran Thi Yen Nhi
Ho Chi Minh city - 2023
Gas chromatography
Gas chromatography (GC) is used for separating and analyzing
compounds that can be vaporized without decomposition.
The compounds are separated primarily by the differences in
their volatilities and structures (polarity)
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INTRODUCTION
https://www.youtube.com/watch?v=C2BJ5DwFk7o
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What Types of Compounds are Suitable for GC Analysis?
• All or a portion of the compound molecules have to be in the
gaseous or vapor state below 400 °C without decomposition
• Compound structure and molecular weight can be used as indicators of
potential GC analysis suitability
• E.g. Some small molecules such as sugars and amino acids can not be easily analyzed by
GC due to a large number of polar groups
3
Which factors influence the separation of the analytes?
§The boiling point of analytes
☞ Higher boiling point -> higher retention time
§The similarity of the polarity of analytes and SP
☞ The more the difference in polarization -> less retention time
§Column temperature
☞ High column temperature -> less retention time
§Carrier gas flow rate
☞ High carrier gas flow-> less retention time (Van Deemter curve)
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Interaction: Polar like Polar or Non-polar like Non-polar
Name Descriptions Characteristic Example
All compounds,
London Scale with
non-polar
dispersion molecular size
interactions
Hydrogen
Dipole-dipole Compound
bonding> Dipole-
(induce containing OH or
dipole> Dipole-
dipole) NH, halogen,…
induce dipole 5
Why do compounds 2,5,8,10 have an increased retention time in the non-polar column?
Explanation of the retention time of compounds 9 and 10 in two columns? 6
How does GC work?
Data processor &
system controller
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Carrier gas (mobile phase)
To transport the sample through the system
Ø Chemically inert gases (He, H2, N2)
Ø High purity, 99.9995% pure or better
Ø Detector Compatibility
Ø High Efficiency & speed / Economic & safety reasons
Ø The gas filter must be used to eliminate impurities in carrier
gases such as water, oxygen, and hydrocarbons
8
The relationship between HEPT and carrier gas velocity
☞ Which were the optimum velocities of 3 gases? 9
☞
Thời gian (phút)
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Thời gian (phút)
7
10
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Pressure regulators
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Pressure regulators
Copper tubbing
The triple combination filter
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The split/ splitless injector
To vaporize and mix the sample with the carrier gas
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https://www.youtube.com/watch?v=TaLOF_jVRno
GC liner Glass wool
• Increase surface area-improved vaporization
• Minimize particulate and non-volatile compounds
reaching the column 15
Microsyringes Autosampler
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Liquid-gas phase change involves a significant change in volume.
Gaseous sample volume depends on the solvent type, column head
pressure, temperature of the inlet
Solvent 20psi 5psi
Hexane 139µL 245µL
Methanol 449µL 792µL
Water 1007µL 1774µL
*Calculated Vapor Volume of Selected Solvents 1 µl at 250oC
=> Small volume injection (Recommended injection volumes are 1-2µL or
less for organic solvents, 0.5µL for water) 17
GC Sample Volume
https://www.youtube.com/watch?v=NULlsDM9FQg&t=12s
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Manual injection
https://www.youtube.com/watch?v=xelz9qbi0T8
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Autosampler injection
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GC Sample Discrimination
https://www.youtube.com/watch?v=NULlsDM9FQg&t=12s 21
Solvent effect in Gas chromatography
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Calibration curve
300
6
250
Area compound/Are IS
5 y = 0,0099x - 0,044
R² = 0,9984
200
4
Area
150
3
100 2
50 1
0 0
0 200 400 600 0 100 200 300 400 500 600
-50 -1
Concentration of Analyte (ppm) Concentration of Analyte (ppm)
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Error due to injection sample volume
Stt Name Re.Time Area Compare %RSD of peak area A and peak
A 3.282 100.3 area ratio A/B in three replicate
1 injection?
B 4.517 122 !"∗$%%
%RSD= &'(
Stt Name Re.Time Area Internal Standards
A 3.277 168.4
2 - A substance that is similar to the analyte
B 4.515 216.7
- Not present in the sample
- It is added in a constant amount to the
blank, the standards, and the samples
Stt3 Name Re.Time Area
A 3.264 180.9
3
B 4.508 236.5
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Stationary phase
- Two types: Gas-solid chromatography GSC (a solid adsorbent serves as the
stationary phase). Gas-liquid chromatography GLC (a liquid spread on an inert
support or coated as a thin film onto the wall of a capillary column).
Capillary column
Column oven
± 0.2°C in time and ± 1.0°C in space 26
GSC Stationary phase properties
• In GSC mechanism separation is dominated by surface adsorption
interactions.
• Application in the analysis of fixed gases, volatile hydrocarbons,
halocarbons, solvents, and sulfur gases (compounds containing < 12 C
and with a boiling point < 200°C),…. Ex: CO, NO, CH4, SO2,…
• Stationary phases: Inorganic oxide adsorbents, Carbon adsorbents,
molecular sieves, porous polymers,…
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Capillary Column
a plastic capable of withstanding 350oC
• Internal Diameter: 0.1, 0.25, 0.32, 0.53 mm
• Length: 5 to 100 m (most commonly 30 m)
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WCOT PLOT
Film thickness: 0.5 – 5µm Particle layer thickness: 5 – 50 µm
Internal diameter: 100-530 µm Internal diameter: 320-530 µm
Wall-coated open tubular column Porous-layer open tubular column
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PLOT Column
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GLC Stationary phase properties
- Chemically inert
- Low vapor pressure
- Thermal stability and wide temperature operating range
- Appropriate retention factor and selectivity
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Some types of stationary phase
- The most popular liquid phase in GC was the Poly(siloxane) stationary phase. Poly
(siloxanes) are generally linear polymers with can contain different substituents such as
methyl, vinyl, phenyl, or 3-cyanopropyl,…suitable for compounds of different polarity.
Poly(siloxane) polymer
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Chemical structures of popular Polysiloxanes
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Compare the polarity of the following capillary columns
1.
2.
3.
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Column information
Manufacture, Stationary phase, Length, Initial diameter, film thickness, operation temperature
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General Guide to Selecting Polarity
vSelecting columns with polar properties that are close
to the polarity of the target compounds
v Selection of Internal Diameter (ID), film thickness,…
,…
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Resolution increases in proportion to the square root of the column length
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GC Detector
The ideal detector’s properties:
ü Sensitivity, Selectivity, Stability
ü Wide linear range
ü Give extra information about the chemical structure
ü Fast response, and easy to use
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Common Detectors for GC
Universal Selective
FID – Flame ionization detector ECD-Electron capture detector
TCD-Thermal conductivity detector MS- Mas spectrometry detector
MS- Mas spectrometry detector
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GC-FID
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GC-ECD
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FID Detector
§ A nearly universal
§ High sensitivity, Stability
§ Easy to operate, fast signal response
§ Large linear range.
§ He, Xe, H2, N2, N2O, NO, CO2, CS2, COS, NH3, SO2, etc., water,
and formic acid does not provide a significant detector
response.
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Ion formation results from chemical
ionization of CHO* produced by
reaction of O· and CH·
O· + CH· -> CHO+ + e -
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Which compound gives the most sensitive signal on the FID detector?
1,4-naphthoquinone 7-chloro-1-methylnaphthalene 1-naphthol Naphthalene
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ECD Detector
ECD is particularly sensitive to halogen-containing
molecules, conjugated carbonyls (C=O), nitriles
(–CN), nitro compounds (-NO2) and organometallic
compounds, but relatively insensitive to
hydrocarbons, alcohols, and ketones.
The detector is particularly useful for chlorinated
pesticides and fluorocarbons in environmental
samples.
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BHC Aldrin Eldrin
Methoxychlor
DDT
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MS Detector
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GC-MS configuration
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Ion source
Convert gasous molecules into charge ions by mean of electron bombardment
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GC 7890 FID Agilent
Gas source & PC system
purifiers
Injection Detector
port
Column
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Isothermal and Programmed temperature
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